CN1274932A - Barium titanate semiconductor ceramic powder and stacked semiconductor device - Google Patents
Barium titanate semiconductor ceramic powder and stacked semiconductor device Download PDFInfo
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- CN1274932A CN1274932A CN00117677A CN00117677A CN1274932A CN 1274932 A CN1274932 A CN 1274932A CN 00117677 A CN00117677 A CN 00117677A CN 00117677 A CN00117677 A CN 00117677A CN 1274932 A CN1274932 A CN 1274932A
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- CN
- China
- Prior art keywords
- barium titanate
- base powder
- resistance
- lamination
- barium
- Prior art date
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 37
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 title claims description 39
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003475 lamination Methods 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005524 ceramic coating Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 16
- 239000010953 base metal Substances 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910018879 Pt—Pd Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 organic bond Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/025—Perovskites, e.g. titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/18—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material comprising a plurality of layers stacked between terminals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
A compact and low resistance laminated semiconductor ceramic device which is provided with a positive resistance-temperature characteristic and has a broad resistance-change range and a high breakdown voltage in addition to ohmic contact between semiconductor ceramic layers and internal electrodes is provided. A doped barium titanate semiconductor ceramic having an average particle diameter of not more than about 1.0 mum, a c/a axis ratio of not less than about 1.005, and a barium site/titanium site ratio from about 0.99 to 1.01, in which a donor element, such as lanthanum (La), is used.
Description
The present invention relates to the semiconductive ceramic device of barium titanate [-Base powder and a kind of lamination, the positive resistance-temperature characterisitic that is provided by the semiconductor ceramic coating that forms by sintering barium titanate [-Base powder is provided this ceramic component.
Barium titanate [-Base has positive resistance-temperature characterisitic (positive temperature coefficient characteristics, ptc characteristics), wherein resistivity at room temperature is low, and resistance promptly increases when some temperature (Curie temperature) are above, and this semiconductive ceramic is widely used for temperature control, Current Control, heated at constant temperature etc.In above-mentioned situation, required the over-current protection device miniaturization, have high puncture voltage, and especially, at room temperature have lower resistance.
The device of these requirements has in response been advised a kind of semiconductive ceramic device of lamination in for example 57-60802 day patent application of the present disclosure is open.The semiconductive ceramic device of this lamination is by alternately laminated main by barium titanate semiconductor ceramic coating that constitutes and the internal electrode that is made of platinum-nickel alloys (Pt-Pd alloy), carries out sintering then and obtains.By using the structure of this lamination, can increase the area of internal electrode in the semiconductive ceramic device greatly, therefore, can realize miniaturization of devices.
But, in the semiconductive ceramic device of lamination,,, thus, a problem is arranged so be difficult between internal electrode and semiconductor ceramic coating, obtain ohmic contact because the Pt-Pd alloy is used as internal electrode, that is, the resistance under the room temperature has increased greatly.
In addition, instead the Pt-Pd alloy and be used for internal electrode material, the nickeliferous metal (below be called the Ni Base Metal) such as nickel or nickel-containing alloys has been proposed in 6-151103 Japanese Patent Application Publication for example.The inner conductive material that is made of Ni Base Metal and semiconductive ceramic shows fabulous ohmic contact between internal electrode and semiconductor ceramic coating, the result can prevent that resistance from room temperature increasing.
But, the Ni Base Metal is being used as under the situation of internal electrode material, owing to form Ni Base Metal oxidation rapidly in air in general sintering step of internal electrode, the result, in reducing atmosphere, carried out after the sintering step, owing to oxidation step once more need take place under relatively low temperature, thereby make the not oxidation of Ni Base Metal, problem is 2 orders of magnitude that the resistance variations scope is reduced to not enough size.Correspondingly, its puncture voltage is not enough, so problem is arranged in actual use.
Correspondingly, an object of the present invention is to provide a kind of miniaturization, and the semiconductive ceramic device of low-resistance lamination, this ceramic component has positive resistance-temperature characterisitic, wherein the semiconductive ceramic device of lamination is except the ohmic contact between semiconductor ceramic coating and internal electrode, also present enough variations of resistance and high puncture voltage.
Another object of the present invention provides a kind of barium titanate [-Base powder, and it is advantageously used in the semiconductor ceramic coating that forms in the semiconductive ceramic device that is arranged on above-mentioned lamination.
For this reason, the present inventor finds by long-term further investigation, can possess the barium titanate [-Base powder of certain special properties by use, can access resistance has enough variations, and the semiconductive ceramic device of the miniaturization of high-breakdown-voltage and low-resistance lamination.
That is, the average particle diameter of barium titanate [-Base powder of the present invention is not more than 1.0 μ m, and the c/a axial ratio is less than 1.0050, and barium (Ba) position (site)/titanium (Ti) position wherein is dissolved with donor element than from 0.990 to 1.010.
Even barium titanate [-Base powder of the present invention can be synthetic by various synthetic methods, when by method for hydrolysis synthesis of barium titanate semiconductive ceramic powder, Ba position/Ti position is than preferably from 0.990 to 1.000, and when the solid phase method synthesis of barium titanate semiconductive ceramic powder, Ba position/Ti position is than preferably from 1.000 to 1.010.
The present invention can be applied to be provided with the semiconductive ceramic device of the lamination of the alternately laminated semiconductor ceramic coating of a plurality of internal electrodes and a plurality of and described internal electrode.
In the semiconductive ceramic device according to lamination of the present invention, semiconductor ceramic coating can obtain by the above-mentioned barium titanate [-Base powder of sintering.
In the semiconductive ceramic device of above-mentioned lamination, internal electrode preferably is made of the conductive component that comprises Ni Base Metal (that is the nickeliferous metal such as nickel or nickel-containing alloys).
Fig. 1 is the sectional view that illustrates according to the semiconductive ceramic device 1 of lamination of the present invention.
The semiconductive ceramic device 1 of lamination is provided with element body 4, and this elements body 4 is alternately to form with the stacked a plurality of internal electrodes 2 of a plurality of inner ceramic layer 3 by sintering.On two edge surfaces of element body 4, form outer electrode 5.Outer electrode 5 is connected electrically to specific internal electrode 2 respectively, and is arranged alternately the internal electrode 2 that is connected to an outer electrode 5, and the internal electrode 2 that is connected to other outer electrode 5.
The semiconductive ceramic device 1 of lamination has positive resistance-temperature characteristic, and is used for for example over-current protection device.
Obtain semiconductor ceramic coating 3 by sintering barium titanate [-Base powder.In the barium titanate [-Base powder, when needs, sub-fraction barium can be by calcium (Ca), strontium (Sr), plumbous replacements such as (Pb), and perhaps a fraction of titanium can be by tin (Sn), zirconium replacements such as (Zr).The semiconductor that comprises in the barium titanate [-Base material forms jizi for making dumplings and is called donor element.As donor element, can use rare earth element (such as lanthanum (La), yttrium (Y), samarium (Sm), cerium (Ce), dysprosium (Dy), gadolinium (Gd), etc.), and transition elements (such as niobium (Nb), tantalum (Ta), bismuth (Bi), antimony (Sb), tungsten (W) etc.).In addition, when needs, can be with silica (SiO
2), manganese materials such as (Mn) adds above-mentioned barium titanate [-Base material.
The average particle diameter that is used to form the barium titanate [-Base powder of semiconductor ceramic coating is not more than 1.0um, and the a/c axial ratio is not less than 1.0050, and donor element has wherein been dissolved than from 0.990 to 1.010 in Ba position/Ti position.Do not limit the synthetic method of barium titanate [-Base powder especially; And can use such as hot-water process, hydrolysis, coprecipitation, solid phase method and sol-gel processing, and, when needs, carry out presintering.
By experiment confirm, when by method for hydrolysis synthesis of barium titanate semiconductive ceramic powder, Ba position/Ti position is than preferably from 0.990 to 1.000, and under the situation of using solid phase method, Ba position/Ti position is than preferably from 1.000 to 1.010.
As the conductive component that comprises in the internal electrode 2, the Ni Base Metal be can use, (Mo) metal that contains molybdenum, chromium (Cr) metal and alloy thereof contained, in particular,, preferably use the Ni Base Metal owing to can realize and the reliable ohmic contact of semiconductor ceramic coating 3.
As the conductive component that is comprised in the outer electrode 5, can use silver (Ag), palladium (Pd) and alloy thereof, and compare with the material that is used for internal electrode 2, do not limit metal especially.Below, with reference to an example, describe the present invention in detail.
Example
Below in the table 1 that illustrates, by the barium titanate [-Base powder of method for hydrolysis synthetic sample 1 to 8, by the barium titanate [-Base powder of solid phase method synthetic sample 9 to 20.
For sample 1 to 8,15.40 liters of baryta waters of preparation (contain concentration and are 0.2 mole/liter barium hydroxide (containing 3.079 moles barium) and 7.58 liters of alkoxytitanium solution and (contain concentration and be 0.35 mole/liter alkoxytitanium (containing 2.655 moles titanium) in the groove that separates in advance.Alkoxytitanium solution contains (tetra isopropyl oxide) titanium (Ti (O-iPr)
4), be dissolved in the isopropyl alcohol (IPA).In addition, in above-mentioned preparation,, in alkoxytitanium solution, add 100 milliliters and contain the lanthanum chloride ethanolic solution of (containing 0.00664 mole lanthanum), evenly mix with it then in order to dissolve the lanthanum that forms agent as semiconductor.
Then, the solution in the groove of separating is admixed together, and by static mixer (staticmixer) mixing, thereby begin reaction.Correspondingly, obtain containing the slurry of barium titanate powder, and the slurry that will obtain placed baking oven 3 hours.
The slurry to preservation dewater and rinsing after, 110 degrees centigrade of dryings 3 hours, then carry out pulverization process, thereby obtain containing the barium titanate powder of lanthanum.
By adding brium carbonate (BaCO
3) or titanium dioxide (TiO
2), to have the various ratios of Ba position/Ti position, carry out pre-burned then, and obtain having the barium titanate [-Base powder of the various character of sample as shown in table 11 to 8 for the barium titanate powder that contains lanthanum.
In addition, for sample 9 to 20, measure to start with raw-material specific area from 1 to 20m
2The BaCO of/g
3, specific area from 1 to 50m
2The TiO of/g
2, and samarium nitrate solution, be 0.002 so that make base mole than Sm/Ti, the ball that uses distilled water and diameter to be made of PSZ as 5mm then by ball mill, mixed 5 hours.In preparation process, measure BaCO
3And TiO
2, so that have various Ba position/Ti position ratio.
Solution to above-mentioned mixing evaporates and drying, and the mixed-powder that obtains was calcined 2 hours at 900 to 1,250 degrees centigrade.
After the ball that is used distilled water and diameter to be made of PSZ as 5mm by ball mill is pulverized 5 to 30 hours, evaporate and drying.
As a result, obtain having the barium titanate [-Base powder of the various performances of sample as shown in table 19 to 20.
Table 1
| Barium titanate powder | Device property | |||||
| Sample number | Average particle diameter (μ m) | The c/a ratio | The Ba/Ti ratio | Room temperature resistance (Ω) | Resistance changes scope (purlin) | Puncture voltage (V) |
| ????*1 | ????0.1 | ??1.0045 | ????0.992 | ??0.10 | ????0.6 | ????＜1 |
| ????2 | ????0.2 | ??1.0050 | ????0.992 | ??0.12 | ????3.5 | ????25 |
| ????3 | ????0.3 | ??1.0070 | ????0.992 | ??0.14 | ????3.2 | ????22 |
| ????4 | ????0.3 | ??1.0071 | ????0.994 | ??0.11 | ????3.9 | ????29 |
| ????5 | ????0.4 | ??1.0071 | ????0.994 | ??0.12 | ????3.7 | ????25 |
| ????*6 | ????0.4 | ??1.0072 | ????0.988 | ??0.25 | ????1.5 | ????4 |
| ????7 | ????0.5 | ??1.0076 | ????0.990 | ??0.15 | ????3.0 | ????21 |
| ????8 | ????0.4 | ??1.0074 | ????1.000 | ??0.16 | ????3.3 | ????22 |
| ????9 | ????0.7 | ??1.0070 | ????1.000 | ??0.20 | ????3.5 | ????32 |
| ????10 | ????0.5 | ??1.0070 | ????1.000 | ??0.19 | ????3.5 | ????31 |
| ????11 | ????0.2 | ??1.0050 | ????1.001 | ??0.18 | ????3.6 | ????29 |
| ????12 | ????0.8 | ??1.0080 | ????1.001 | ??0.15 | ????3.7 | ????31 |
| ????*13 | ????1.5 | ??1.0085 | ????1.002 | ??0.10 | ????1.0 | ????2 |
| ????14 | ????1.0 | ??1.0090 | ????1.002 | ??0.10 | ????3.9 | ????29 |
| ????15 | ????0.2 | ??1.0060 | ????1.005 | ????0.10 | ????4.0 | ????30 |
| ????*16 | ????1.5 | ??1.0100 | ????1.002 | ????0.09 | ????0.9 | ????1.5 |
| ????*17 | ????0.1 | ??1.0043 | ????1.004 | ????0.12 | ????0.4 | ????＜1 |
| ????*18 | ????0.88 | ??1.0083 | ????1.013 | ????2.20 | ????2.0 | ????6 |
| ????19 | ????0.85 | ??1.0079 | ????1.010 | ????0.19 | ????3.6 | ????30 |
| ????20 | ????1.0 | ??1.0090 | ????1.010 | ????0.20 | ????3.4 | ????31 |
Use scanning electron microscopy (SEM) photo, obtain the average particle diameter of the gained calcined powder shown in the table 1 by graphical analysis.Obtain Ba position/Ti position than (shown in the Ba/Ti ratio in the table) and c/a axial ratio by x-ray fluorescence analysis and X-ray diffraction pattern respectively.
After adding organic solvent, organic bond, plasticizer or the like are added powder, form each sample, so that preparation contains the pottery of slurry, above-mentioned slurry is handled by the scraping blade method, obtains ceramic green sheet thus.
Form the duplexer that will form element body by following steps: nickeliferous conductive paste is screen-printed on the certain ceramics raw cook, form internal electrode, the stacked raw cook that is provided with internal electrode like this, so that obtain element body as shown in Figure 1, to there be the ceramic green sheet of internal electrode to be layered in its top and bottom, and pressurize, cut the raw cook of whole lamination then.
After in air, removing adhesive, in strongly reducing atmosphere (wherein hydrogen/nitrogen ratio is 3/100), fire 2 hours from these duplexers, thus the element body after obtaining firing.Then, in air, under 600 to 1,000 degrees centigrade, carried out once more oxidation processes 1 hour.Then,, in air, fire then, obtain the semiconductive ceramic device of lamination by silver paste being covered two edge surfaces of element body.All roughly 3.2mm is long for each device that obtains, and 2.5mm is wide, and 1.0mm is thick.
Semiconductive ceramic device to the lamination of formation like this is measured room temperature resistance, resistance variations scope and puncture voltage.Use digital voltmeter, measure room temperature resistance by four probe method.Resistance variations scope (size the order of magnitude) is represented by the common logarithm by the value that will obtain divided by minimum resistance from the maximum resistance of room temperature to 250 degree centigrade.The maximum voltage that puncture voltage applies before just being damaged by device is represented.The results are shown in the table 1.
In table 1, the sample number of beating asterisk is outside scope of the present invention.
With reference to table 1, when average particle diameter is not more than 1.0um, the c/a axial ratio is not less than 1.0050, and Ba position/Ti position was than from 0.990 to 1.010 o'clock (as 2 to 5,7 to 12,14,15,19 and 20 samples), its room temperature resistance of the device that obtains is not more than 0.20 ohm, the resistance variations scope is not less than 3 orders of magnitude of size, and puncture voltage is not less than 20 volts.
By contrast, when the average particle diameter of barium titanate powder surpasses 1.0um (as in 13 and 16 samples), low 3 orders of magnitude of the resistance variations of the device that obtains less than size, and puncture voltage is reduced to 2 volts.
When as in sample 1 and 17, the c/a axial ratio was less than 1.0050 o'clock, the resistance variations scope of the device that obtains is very little, and puncture voltage also reduces greatly.
When as in sample 6 and 18, Ba position/Ti position is than respectively less than 0.990 or greater than 1.010 o'clock, and the room temperature resistance of the device that obtains increases, and resistance variations scope and puncture voltage reduce greatly.
In the sample 1 to 8 that obtains by use method for hydrolysis synthesis of barium titanate powder, sample 2 to 5,7 and 8 illustrates advantageous characteristic, Ba position/Ti position is than from 0.990 to 1.000, in the sample 9 to 20 that uses the barium titanate powder synthetic to form by solid phase method, sample 9 to 12,14,15,19 and 20 illustrates advantageous characteristic, and Ba position/Ti position is than from 1.000 to 1.010.
As mentioned above, the average particle diameter of barium titanate [-Base powder of the present invention is not more than 1.0um, and the c/a axial ratio is not less than 1.0050, and donor element has wherein been dissolved than from 0.990 to 1.010 in Ba position/Ti position.Thereby the semiconductive ceramic device of the lamination by firing the semiconductor ceramic coating that the barium titanate [-Base powder obtains is small-sized, and has low resistance, and has enough resistance variations scopes, in addition, has high puncture voltage.
Especially, when barium titanate [-Base powder of the present invention produces by method for hydrolysis and solid phase method respectively, in the Ba position/Ti position ratio is 0.990 to 1.000, and under 1.000 to 1.010 the situation, can obtain above-mentioned superior characteristic reliably.
In the semiconductive ceramic device of lamination, when internal electrode comprises nickel, can reach the ohmic contact between internal electrode and the semiconductor ceramic coating reliably.
Claims (5)
1. barium titanate [-Base powder, its average particle diameter is not more than 1.0um, and the a/c axial ratio is not less than 1.0050, and barium position/titanium position ratio from 0.990 to 1.010,
It is characterized in that, in described barium titanate [-Base powder, dissolved donor element.
2. barium titanate [-Base powder as claimed in claim 1 is characterized in that, described barium titanate [-Base powder is synthetic by method for hydrolysis, and barium position/titanium position ratio from 0.990 to 1.010.
3. barium titanate [-Base powder as claimed in claim 1 is characterized in that by the synthetic described barium titanate [-Base powder of solid phase method, and barium position/titanium position ratio from 1.000 to 1.010.
4. the semiconductive ceramic device of a lamination is characterized in that comprising:
A plurality of internal electrodes; With
The alternately laminated semiconductor ceramic coating of a plurality of and described internal electrode;
Wherein, described semiconductor ceramic coating forms by sintering such as each described barium titanate [-Base powder of claim 1 to 3.
5. the semiconductive ceramic device of lamination as claimed in claim 4 is characterized in that internal electrode comprises nickel.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13978199 | 1999-05-20 | ||
| JP139781/1999 | 1999-05-20 | ||
| JP2000046122A JP3812268B2 (en) | 1999-05-20 | 2000-02-23 | Multilayer semiconductor ceramic element |
| JP46122/2000 | 2000-02-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1274932A true CN1274932A (en) | 2000-11-29 |
| CN1215485C CN1215485C (en) | 2005-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001176773A Expired - Lifetime CN1215485C (en) | 1999-05-20 | 2000-05-22 | Barium titanate semiconductor ceramic powder and stacked semiconductor device |
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| Country | Link |
|---|---|
| US (1) | US6542067B1 (en) |
| JP (1) | JP3812268B2 (en) |
| KR (1) | KR100364969B1 (en) |
| CN (1) | CN1215485C (en) |
| DE (1) | DE10024821B4 (en) |
| GB (1) | GB2350108B (en) |
| TW (1) | TW476075B (en) |
Cited By (5)
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| CN100373508C (en) * | 2002-10-30 | 2008-03-05 | 株式会社村田制作所 | Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor |
| CN101401172B (en) * | 2006-03-10 | 2011-01-26 | 卓英社有限公司 | Ceramic component element and ceramic component and method for the same |
| CN101268527B (en) * | 2005-09-20 | 2011-04-27 | 株式会社村田制作所 | Multilayer positive coefficient thermistor |
| CN101717243B (en) * | 2003-11-12 | 2013-02-27 | 联邦莫沃尔公司 | Ceramic with improved high temperature electrical properties for use as a spark plug insulator |
| CN107210105A (en) * | 2015-02-06 | 2017-09-26 | 株式会社村田制作所 | Semiconductor element and its manufacture method |
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| WO2002091408A1 (en) * | 2001-05-08 | 2002-11-14 | Epcos Ag | Ceramic multi-layer element and a method for the production thereof |
| US7431911B2 (en) | 2001-07-04 | 2008-10-07 | Showa Denko K.K. | Barium titanate and production and process thereof |
| US20040121153A1 (en) * | 2002-12-20 | 2004-06-24 | Sridhar Venigalla | High tetragonality barium titanate-based compositions and methods of forming the same |
| JPWO2005016845A1 (en) * | 2003-08-14 | 2007-10-04 | ローム株式会社 | Dielectric ceramic composition, multilayer ceramic capacitor, and electronic component |
| WO2007034831A1 (en) | 2005-09-20 | 2007-03-29 | Murata Manufacturing Co., Ltd. | Stacked positive coefficient thermistor |
| TW200733159A (en) * | 2006-02-24 | 2007-09-01 | Wei-Hsing Tuan | Ceramic dielectrics and base-metal-electrode multilayer ceramic capacitors |
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| KR101178971B1 (en) * | 2008-12-12 | 2012-08-31 | 가부시키가이샤 무라타 세이사쿠쇼 | Semiconductor ceramic and positive temperature coefficient thermistor |
| CN102245536B (en) * | 2008-12-12 | 2013-07-31 | 株式会社村田制作所 | Semiconductor ceramic and positive temperature coefficient thermistor |
| JP5510455B2 (en) * | 2009-07-01 | 2014-06-04 | 株式会社村田製作所 | Semiconductor ceramic and positive temperature coefficient thermistor |
| JP6065303B2 (en) | 2012-06-15 | 2017-01-25 | ローム株式会社 | Switching device |
| WO2016125519A1 (en) * | 2015-02-06 | 2016-08-11 | 株式会社村田製作所 | Semiconductor element and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5760802A (en) * | 1980-09-30 | 1982-04-13 | Tokyo Shibaura Electric Co | Current limiting resistance element |
| JPH0335503A (en) * | 1989-06-30 | 1991-02-15 | Daido Steel Co Ltd | Manufacture of ptc thermistor |
| US5445806A (en) * | 1989-08-21 | 1995-08-29 | Tayca Corporation | Process for preparing fine powder of perovskite-type compound |
| JPH0653011A (en) * | 1992-07-28 | 1994-02-25 | Murata Mfg Co Ltd | Barium titanate based semiconductor porcelain having negative resistance temperature characteristic |
| JP3438736B2 (en) * | 1992-10-30 | 2003-08-18 | 株式会社村田製作所 | Manufacturing method of laminated semiconductor porcelain |
| US5820995A (en) * | 1995-10-27 | 1998-10-13 | Murata Manufacturing Co., Ltd. | Laminated composite ceramics and elements using same |
| DE19902153B4 (en) * | 1998-01-20 | 2005-03-10 | Murata Manufacturing Co | Process and barium titanate powder for the production of dielectric ceramic |
| DE19902151B4 (en) * | 1998-01-20 | 2005-03-10 | Murata Manufacturing Co | Process for the preparation of a dielectric ceramic and barium titanate powder for such a process |
-
2000
- 2000-02-23 JP JP2000046122A patent/JP3812268B2/en not_active Expired - Lifetime
- 2000-05-17 GB GB0011922A patent/GB2350108B/en not_active Expired - Lifetime
- 2000-05-18 TW TW089109575A patent/TW476075B/en not_active IP Right Cessation
- 2000-05-18 KR KR1020000026667A patent/KR100364969B1/en active IP Right Grant
- 2000-05-19 DE DE10024821A patent/DE10024821B4/en not_active Expired - Lifetime
- 2000-05-22 US US09/575,581 patent/US6542067B1/en not_active Expired - Lifetime
- 2000-05-22 CN CNB001176773A patent/CN1215485C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100373508C (en) * | 2002-10-30 | 2008-03-05 | 株式会社村田制作所 | Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor |
| CN101717243B (en) * | 2003-11-12 | 2013-02-27 | 联邦莫沃尔公司 | Ceramic with improved high temperature electrical properties for use as a spark plug insulator |
| CN101268527B (en) * | 2005-09-20 | 2011-04-27 | 株式会社村田制作所 | Multilayer positive coefficient thermistor |
| CN101401172B (en) * | 2006-03-10 | 2011-01-26 | 卓英社有限公司 | Ceramic component element and ceramic component and method for the same |
| CN107210105A (en) * | 2015-02-06 | 2017-09-26 | 株式会社村田制作所 | Semiconductor element and its manufacture method |
| CN107210105B (en) * | 2015-02-06 | 2019-09-03 | 株式会社村田制作所 | Semiconductor element and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10024821B4 (en) | 2006-03-30 |
| GB2350108A (en) | 2000-11-22 |
| GB2350108B (en) | 2001-07-18 |
| CN1215485C (en) | 2005-08-17 |
| JP2001031471A (en) | 2001-02-06 |
| KR100364969B1 (en) | 2002-12-16 |
| DE10024821A1 (en) | 2000-12-07 |
| TW476075B (en) | 2002-02-11 |
| US6542067B1 (en) | 2003-04-01 |
| KR20010049365A (en) | 2001-06-15 |
| GB0011922D0 (en) | 2000-07-05 |
| JP3812268B2 (en) | 2006-08-23 |
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